Monoazophthalocyanine dyes



, assess Patented Get. 23, 1952 Sire 3,059,988 MUNOAZOPHTHALOCYANKNEDYES Eugen J. Koller, Binningen, and Hugo Illy, Basel, Switz erland,assignors to Ciba Limited, Basel, Switzerland No Drawing. Filed Dec. 4,1959, Ser. No. 857,276 Claims priority, application Switzerland Dec. 18,1958 3 Claims. (Cl. 8-26) NHOOR (I) in which R represents a vinyl or3-halogen-ethyl group. More especially, this invention providesdyestuffs of the general formula in which Pc represents the radical of aphthalocyanine group, A represents a divalent organic radical, Xrepresents an azoor iminolinkage, m represents a Whole number within therange of 1-5, n represents the whole number 1 or 2, 12 represents awhole number of at least 2, q the whole number 1 or 2, and R has thesame meaning as that given above. The benzene radical B may be bounddirectly or through the bridge A-X to the phthalocyanine-sulfonamidogroup. A preferably represents the radical of a coupling component, forexample, a benzene or aceto-acetic-arylide, or A is a heterocyclicradical, especially the radical of a l-phenylpyrazolone-(S).

The present invention also provides a process for the manufacture of theabove dyestuffs, wherein a sulfonic acid halide or a phthalocyaninedyestuff is condensed with an organic compound containing an acylatibleamino group, the uncondensed sulfonic acid halide groups are thenhydrolyzed, and the condensation product thus obtained is, if desired,coupled with a diazo component, the reaction components being so chosenthat the dyestuif produced contains at least two sulfonic acid groups,and one group of the Formula I.

As starting materials for the present process, there may be usedmetal-free or metalliferous phthalocyanines such, for example, as thezinc, cobalt, nickel, and especially the copper phthalocyanines.Especially useful compounds are the copper phthalocyanines containingsulfonic acid groups. Depending on Whether 4-sulfophthalic acid is usedas starting material for making these sulfonated phthalocyaninecompounds, or whether these are obtained by sulfonation orsulfochlorination of copper phthalocyanine, the sulfonic acid groups inthe resulting phthalocyanine molecule are in the 4- or 3-positionrespectively. The phthalocyanine compound used as starting material thatmay also contain a sulfonic acid group, must contain at least onesulfonic acid halide group. Such a sulfonic acid halie compound may beobtained, for example, by reacting a phthalocyanine trior tetra-sulfonicacid with an agent capable of forming acid halides, such, for example,as a phosphorous halide, thionyl chloride or chlorosulfonic acid, and bypartially hydrolyzing the sulfa-halide thus obtained.

The resulting starting material is treated with an organic compoundcontaining an acylatible amino or hydroxyl group, for example, with acompound of the general formula NHOOR I NHCOR in which R has the meaninggiven above, and in which the benzene radical may contain othersubstituents such, for example, as alkyl groups or halogen atoms, andblue dye-stuffs are thus obtained.

The compounds of Formula III may be obtained by reduction of thecorresponding nitro-compounds under conditions such that the acid groupsare not split oil, advantageously by catalytic hydrogenation. Thenitro-cornpounds may be obtained according to the process of US.specification No. 2,475,846, by condensation of one molecular proportionof a Intro-aldehyde with 2 molecular proportions of B-chloro-propionicacid amide or acrylic acid amide, in the presence of a strong acid,especially hydrochloric acid or sulfuric acid.

The phthalocyanine sulfochlorides may, be condensed with a couplingcomponent, from containing a coupling group, also contains an acylatibleamino group, and the condensation product thus obtained is coupled witha diazo compound containing the group CH(NHCOR) advantageously with thediazo compounds of the amines of Formula III. In this manner, greendyestuffs are obtained. As coupling components containing an acylatibleamino group, there may be used an amino phenol for example, 1:3 or1:4-amino-phenol, an amino-aceto-acetic-arylide, for example, 1-amino-3-or 4-aceto-acetic anilide, an amino pyrazolone, especially a1-amino-phenyl-5-pyrazolone such, for example, as 3'- or4'-amino-phenyl-3-methyl pyrazolone-S or 3'- or 4-aminophenyl-3-carboxypyrazolone-S, and these coupling components may also contain a sulfonicacid group bound to the benzene radical.

Advantageously, the coupling component is heated before the couplingreaction, in a weakly alkaline medium until any sulfochloride groupsstill present have been completely hydrolyzed. The coupling reactionwith the diazo compound is advantageously carried out in a Weakly acid,neutral or alkaline medium, for example, in a medium containing analkali metal bicarbonate and preferably in the cold.

The dyestuffs obtained by the present process are useful for colouringor printing a very wide variety of materials, especiallypolyhydroxylated fibrous materials, such, for example, as cellulosefibers or synthetic fibers, such for example, as those derived frompolyvinyl alcohol, regenerated cellulose, and also for colouring orprinting natural products, for example, linen and especially cottonmaterials. The dyestuffs may be used either in the so-calletl directdyeing method or in a printing or pad-dyeing process, in which thematerial that is to be alternatively, which, apart dyed is treated withthe dyestuif which is then fixed by a heat treatment, for example, asteam treatment in the presence of an alkali. Advantageously, thefixation of the dyestufi on the material is carried out in the presenceof a fairly strong alkali such, for example, as an alkali metalhydroxide, so that an improved fixation of the dyestuff is obtained.Thus, good results are obtained by carrying out the fixation in a mediumhaving a pH-value greater than 9, but still better results are obtainedin a medium having a pH-value above 10.

The dyeings on cellulosic fibers, with the dye-stuffs of this invention,are distinguished by the purity of their tints, their good fastness tolight and, above all, by their good fastness to washing.

In certain cases, it may be of advantage to after-treat the dyeingsobtained in the above manner. Thus, for example, the dyeings mayadvantageously be soaped whereby any unfixed dyestuff is completelyremoved.

The dyestuff of this invention may also be used for dyeing and printingnitrogen-containing materials, such, for example, as leather, silk andespecially woolen materials containing nitrogen, and above all fordyeing and printing fibers of a super polyamide or of a superpolyurethane in weakly alkaline media.

The dyeings on wool have an excellent fastness to washing and fulling.

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise indicated, and therelationship of parts by weight to parts by volume being the same asthat of the gram to the cubic centimeter.

Example 1 288 parts of copper phthalocyanine are stirred into 275 partsof chlorosulfonic acid at such a rate that the temperature does not riseabove 30 C., and the reaction mixture is stirred on for /2 hour at roomtemperature, heated within 1 /2 hours to an internal temperature of 130to 133 C. and stirred for 4 hours at the same temperature. The mixtureis allowed to cool and vigorously stirred into a mixture of 250 parts ofwater, 140 parts of sodium chloride and 1500 parts of crushed ice. Itmust be ensured that the temperature does not rise above 3 C. duringthis operation. The reaction mixture is stirred for a short time,filtered and washed on the suction filter with a mixture of 300 parts byvolume of saturated sodium chloride solution and 150 parts of ice.

The resulting sulfochloride, in the form of an acid paste, is stirredwith 150 parts of ice and adjusted with dilute, cold sodium hydroxidesolution to a pH value of 6.5 to 7.0.

16 parts of the compound of the formula are dissolved with heating in280 parts by volume of acetone, and this solution is added to thethoroughly stirred, neutralized sulfochloride paste. Immediately, 25parts by volume of pyridine are added and the whole is stirred for 24hours at room temperature. Addition of concentrated hydrochloric aciduntil a distinct acid reaction to Congo red is reached precipitates thedyestuff which is filtered ofr, pasted with water, adjusted with dilutesodium hydroxide solution to a pH value of 7.5 and made up to 1000 partsby volume with water. The mixture is stirred for some time at 30 to 40C. While maintaining a weakly alkaline reaction, whereupon all buttraces of the dyestuff passes into solution. The solution is filtered.The dyestufi is salted out with sodium chloride from the filtrate,filtered and then dried in vacuo.

The dyestufi obtained in this manner produces on cot- .4. ton andviscose rayon by the method described in Example 6 a turquoise printwhich is fast to washing.

A similar dyestufi is obtained by using the sulfochloride described inExample 2 and condensing it with metaaminobenzylidene di Bchloropropionylamide as described in Example 1.

Example 2 A mixture of 28.8 parts of copper phthalocyanine and 155 partsby volume of chlorosulfonic acid is thoroughly stirred and heated within1 to 1 /2 hours to 140 C., and then kept for 2 hours at 138 to 140 C.,allowed to cool to to C. and slowly treated dropwise with 25 parts byvolume of thionyl chloride, then heated to to 93 C. and stirred for 3hours at the same temperature.

The reaction mixture is poured into a mixture of parts of sodiumchloride and 1500 parts of ice and water, filtered, and the filterresidue is thoroughly washed with ice water.

The sulfochloride is turned with 75 parts of water and 75 parts of iceinto a fine paste by stirring and then adjusted with dilute sodiumhydroxide solution at 0 C. to a pI-I value of 7 to 7.3.

44 parts of l-(3'-aminophenyl)-5-pyrazolone-3-carboxylic acid aredissolved under neutral conditions with addition of 20 parts of sodiumcarbonate in parts of water, and the whole is added to the neutralizedsulfochloride paste. 20 parts by volume of pyridine are added to thereaction mixture and the whole is stirred for 24 hours at roomtemperature.

To isolate the dyestuif the cold solution is adjusted with concentratedhydrochloric acid to an acid reaction to Congo red andthe precipitatedproduct is filtered 01f. To remove any uncondensed aminophenylpyrazolonecomponent as far as possible, an alkaline solution of the dyestulf isprepared, from which it is again precipitated with hydrochloric acid andfiltered oil, then again dissolved in water at a pH of 6 to 6.6 andtreated with heating under weakly alkaline conditions until anyremaining sulfochloride groups have been hydrolyzed. The dyestuff isthen salted out at 60 to 65 C. with sodium chloride, filtered andwashed.

This coupling component is dissolved in 500 parts of water with additionof 50 parts of sodium bicarbonate. 31.8 parts ofmeta-aminobenzylidene-di-fi-chloropropionylamide are diazotized in theusual manner With hydrochloric acid and sodium nitrite. This diazoniumsolution is slowly added at 0 to 10 C. to the above alkaline solution ofthe coupling component. On completion of the coupling the precipitatinggreen dyestuff is filtered off. To convert it into a readilywater-soluble form it is stirred with cold water, dissolved withaddition of 35 parts by volume of N-sodium hydroxide solution and turnedinto a solid powder in a spray-drier.

When cotton is printed with this dyestuff by the method described inExample 6, brilliant green tints fixed fast to washing are obtained.

When applied as described in Example 7, the dyestufi produces dyeingsthat are fast to washing.

Example 3 28.8 parts of copper phthalocyanine are added with cooling to141 parts by volume of chlorosulfonic acid. The mixture is stirred for 1hours at 70 to 75 C. and in the course of 1 /2 hours raised to 130 to132 C. and stirred at the same temperature for 4 hours, cooled to 80 C.and in the course of 1 hour treated dropwise with 60 parts by volume ofthionyl chloride and then stirred on for 1 hour at 70 to 80 C. Themixture is then cooled to room temperature and poured over ice. Thecopper phthalocyanine sulfochloride is suc-tioned off and thoroughlywashed with ice water. The filter cake is pasted with ethanol, filtered,washed with ethanol and dried in vacuo at 60 C.

With cooling and stirring the above sulfochlcride is added to a solutionof 66 parts of ortho-benzenesulfonate ofl-[3-aminophenyl]-3-methyl-5-pyrazolone in 200 parts of pyridine, andthe reaction mixture is stirred for 24 hours at room temperature, pouredinto 800 parts by temperature and worked up by being poured intoethanol, suction-filtered and the product is thoroughly washed on thefilter with ethanol.

The dyestufi is dissolved in water with addition of exvolume of ethanol,filtered and washed with ethanol. To 5 cess sodium hydroxide solutionand a small amount of hydrolyze the orthobenzenesulfonate grouping thedyepyridine. stuff is heated for 1 hour at 80 to 90 C. with 400 parts Atthe same time 6.4 parts of meta-aminobenzylideneby tvoLume 1of anlgl-sodiclllm hyrll goxige solgtiou and 16 di-fi-chlogonropionjylamlidearef dissolved in:1 pagtls of par 5 y v0 ume o pyri me. e yestu PI'CClPlates Water an parts yvo ume o concentrate y me oric on addition ofconcentrated hydrochloric acid; it forms acid and in the cold diazotizedwith 20 parts by volume a coupling component which is coupled at 0 to 10C., of an N-sodium nitrite solution. This diazonium comin the form of anaqueous solution and in the presence pound is slowly added to thecoupling component preof excess sodium carbonate, with the diazoniumcompared as described above, and on completion of the coupound preparedby diazotizing 21 parts of 3-arninobenzpling the pH is adjusted to 7. Inthe cold 20 parts by ylidene-di-acrylamide with hydrochloric acid andsodium volume of N-sodium hydroxide solution are added, and nitrite. Oncompletion of the coupling the precipitated the product is dried in aspray-drier. dyestuff which is the mixture of about 60% of the Theresulting dyestufi produces on cotton by the method diazophthalocyanineand 40% of the monoazophthalodescribed in Example 6 green prints thatare fast to cyanine dyestufr is filtered off and dried in vacuo.Washing.

When the 3-aminobenzylidene-di-acrylamide is re- Example 6 gi aneqiuvarnt zillount 9 i A solution of 30 parts of the dyestuif obtainedin Ex- 'gi' i pi afifi a i a g. bresu ample 2 in 339 parts of Water istreated with 150 parts n case 1 m Wa er 15 ac W y of urea, the whole ispoured into 450 parts of a sodium veltmg the dyestufl Its enolajteform.wlth the theo' 25 alginate thickener, and the mixture is treatedwith parts retlcal amount of sodium hydroxide solution and further ofpotassium carbonate and 1 part of sodium hydroxide worklllng 1t up i a Pif solution of 40% strength. A cotton fabric is printed in 2 en i 1s mWit g g. dasfcnbed the usual manner with the resulting printing pasteand m S e green m s are 0 tame W 10 are ast to then dried, steamed for 5minutes at 100 to 101 C., rinsed, was ing. Example 4 3O soaped, againrinsed and finally dried. This procedure yields brilliant green prints.24.6 parts of the sodium salt of copper phthalocyanine- Example, 73:4':4:4"'-tetrasulfonic acid are added to 75 parts by volume ofchlorosulfonic acid, and the reaction mixture 5 Parts of P dyfifstllfi Pp as described in E amis heated to 80 to 83 C. with thorough stirring.In the P are m1ed Wlth 80 Parts of trisodl'um Phosphate course of 1 hour27 parts by volume of thionyl chloride and qg 111 Eggg of gs and F 5 i;made are added dro Wise, the mixture is allowed to react for P W1 Waterto P Parts 0 50311111 lofide 4 hours at 80 20 85 0. and thesulfochloride is poured are added, and parts of a cotton n' are i mersedover ice in the usual manner, suctioned ofl? and washed i resultgg g hgg p is raised Within with ice Water on the filten 40 2 our to ano erparts 0 sodium chloride The sulfochloride is turned with ice into a finepaste added: the temperature is Taised t0 i in 1 and while cold adjustedwith dilute sodium hydroxide mmutes, and the Whole is kept at thismmpefatufe for solution to a pH value of 7.0. 8.3 parts ofmetaaminohour; The dy is then rinsed and Soaped for 15benzylidene-di-{i-chloropropionylamide are dissolved with mlnutes 111'bollmg solutlon of a HOB-ionic deterheating in 130 parts of volume ofacetone, the solution m- The dyed fabnc dlsplays excellent fastness Ppis added to the neutralized sulfochloride paste and the arms; whole isimmediately treated with 22 parts by volume A slmllarly good result 1Sach1eVe 1 when in above of pyridine. The mixture is allowed to react for48 hours eXa-mpk Sodlum carbonate 15 used Instead of msodillm at roomtemperature and While cold acidified with conphosphalecentratedhydrochloric acid. The precipitated dyestutf 50 What 15 clalmed, isturned with saturated sodium chloride solution into a Phthalocyanmedyestufi of the formula filterable form and suctioned off. The dyestutfis then 0 stirred With ice and adjusted with dilute sodium hydroxide 1;solution to a pH value of 8, and then salted out with N O M sodiumchloride at 40 C. (Q SONH OH-N=N HN'O R On being printed on cotton asdescribed in Example 6, H this dyestufi produces blue tints which arefast to washl l SOaH)4m i .1.

Example 5 h w erein Q represents the copper phthalocyanine radical, 19.4parts of dry copper phthalocyamne-S:3:3":3 R represents a memberselected from the group consisttetrasulfochloride are stirred withcooling into a solution ing of vinyl and ,B-chloroethyl, m: represents awhole posiof 5.65 parts of 1-am1no-2-meth0Xy-4-acetoacetylammotiv numberup to 2 and X is a member selected from the S-chlorobenzene 1n parts byvolume of pyrldme. group consisting of a lower alkyl and a carboxygroup.

The reaction mixture is stirred for 24 hours at room 2. The dyestufi ofthe formula 000E N= 5 Q SOg-NH N\ NHCOCHnCHr-Cl I C-CHN=N 0 I ONH-OOCH2GHQ-O1 s wherein Q is the copper phthalocyanine radical whichbears the SO groups in the 3, 3, 3", 3" positions.

3. The mixture of the dyestufi of the formula 8 wherein Q is the copperphthalocyanine radical which bears the SO groups in the 3, 3', 3" and 3"positions.

NCO NHCOCH=OH2 \CHN=N- CH N=O \NHOOGH=OH2 Os-OH): H3 2 with the dyestufiof the formula Q SOr-NH- N-CO NHOOCH=CH2 l CH-N=N -O 1 =0 \NHGO-CH=OH2(Son-OHM Ha References Cited in the file of this patent UNITED STATESPATENTS 2,863,875" Bienert et a1. Dec. 9, 1958 FOREIGN PATENTS 218,807Australia Nov. 18, 1958 Guthrie: American Dyestufi Reporter, January 7,

1952 pages 13, 14 and 30.

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3. THE MIXTURE OF THE DYESTUFF OF THE FORMULALA